JP2000284425A - Production of granule - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a process for producing granules which is excellent in continuous production stability and allows mass production with a large-sized granulating machine by adding specific compounds at the time of agitation granulation. SOLUTION: In the process for producing the granules by agitation granulation, at least one kind of the compounds expressed by formulas I, II, etc., are incorporated into the granules at the time of agitation granulation. In the formula I, Rf denotes a saturated or unsaturated alkyl group containing a fluorine atm; X0 denotes sulfone amide, etc.; Y0 denotes an alkylene oxide group, alkylene group and A denotes -SO3M, -OSP3M, etc. M denotes H, Li, K, Na or NH4; m denotes 0, 1 and n denotes an integer from 1 to 10. In the formula II, R1 denotes an alkyl group, alkenyl group; R2 denotes a hydrogen atom, alkyl group or hydroxyalkyl group; R3 and R4 denote hydrogen atoms, hydroxyl groups, alkyl groups, etc.; X denotes -CO-, -SO2-; Y denotes -O-, -S-, etc.,; M3 denotes a hydrogen atom, alkaline metal atom; 1 denotes 0, 1; m1 denotes an integer from 0 to 2 and n1 denotes an integer from 1 to 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing granules, and more particularly to a method for producing granules used for a silver halide solid processing agent by a stirring granulation method, which has excellent storage stability and excellent solubility. The present invention also relates to a method for producing a granular or tablet-like solid processing agent for a silver halide photographic light-sensitive material, which is inexpensive and has excellent stability even in continuous production.

[0002]

2. Description of the Related Art Silver halide color photographic materials (hereinafter also simply referred to as photographic materials or photographic materials) are usually
After exposure, it is processed by steps such as color development, desilvering and stabilization. The black-and-white silver halide photographic material is developed and fixed after exposure. Black and white developer, color developer, bleaching solution, bleach-fixing solution for desilvering process, fixing solution for fixing process, tap water or ion exchange water for washing, stabilizing solution for anhydrous washing, A stabilizing solution is used for the dye stabilization treatment.

A liquid having a processing function for performing each of these processing steps is called a processing liquid. Each processing solution is usually 30
The temperature is adjusted to -45 ° C, and the photosensitive material is immersed in these processing solutions for processing.

Such processing is usually carried out by sequentially transporting the photosensitive material in a processing tank containing the above-mentioned processing solution by an automatic developing machine (hereinafter also referred to as an automatic developing machine) or the like.

Here, an automatic developing machine has a developing section, a fixing section, a desilvering section, a washing or stabilizing section and a drying section.
Refers to a developing machine having means for automatically transporting the photosensitive material sequentially through each processing tank.

[0006] In the case of processing with such an automatic developing machine, a method of replenishing a processing agent is generally employed in order to keep the activity of a processing solution in a processing tank constant.

As a processing agent replenishment method, there is a method in which a replenisher in which a processing agent is dissolved is prepared in advance. There is also a method in which a refill tablet is directly charged into a filter tank directly connected to a processing tank, as in an eco-jet system manufactured by Konica Corporation.

The former method of preparing a replenisher in advance includes a liquid replenisher, a granule replenisher and a tablet replenisher.

It is known that granule replenishers, tablet replenishers and ECOJET tablet replenishers (hereinafter also referred to as solid processing agents) have very excellent stability and are easy to use as compared with liquid replenishers. I have.

[0010] However, these solid processing agents have many problems in production stability from the viewpoint of production, even if they are convenient when used by customers. For example, photographic processing agents must be water soluble in the material itself. Therefore, in agitated granulation, frictional heat is generated by stirring, and when water is added as a liquid binder, heat of dissolution is generated, raising the temperature of the granules themselves and dissolving a part of the granules. Granulation is not stable due to adhesion to the wall or bottom surface of the granulator. Not only is it not stable, but the whole granules solidify in a rice cake-like form, which makes handling in the next process worse, or even makes it impossible to remove it from the granulator,
Problems such as the stoppage of the stirring blade overload and the bending of the stirring blade have occurred. This tendency is particularly remarkable when granulation is performed continuously, and in order to solve this problem, it is necessary to wash or wipe the granulator between batches during production. Furthermore, such a rise in the temperature of the granules becomes remarkable as the batch scale of the granulator is increased, and mass production by a large-sized granulator cannot be performed at once. As a result, there was a major problem that the cost was increased from the viewpoint of production efficiency. In addition, when the granules partially dissolved by the heat generation are used as the granules or compressed into a tablet-like photographic processing agent, there is a problem that the photographic performance when stored for a long time is deteriorated. . Further, the tablet-type photographic processing agent has a problem that the dissolution time is prolonged. In addition, since it is a water-soluble material, high-speed continuous tableting cannot be performed due to problems such as stickiness of the punch and sticking of the punch at the time of tableting.

[0011]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing granules which is excellent in continuous production stability and can be mass-produced by a large-sized granulator when producing granules by a stirring granulation method. In particular, an object of the present invention is to provide an inexpensive production method which is excellent in high-speed continuous productivity of a granular or tablet-like solid processing agent for a silver halide photographic light-sensitive material having excellent storage stability and excellent solubility. It is in.

[0012]

The above object of the present invention is achieved by the following constitution.

(1) A method for producing granules by stirring granulation, wherein at least one of the compounds represented by the following general formulas (I) to (VI) is added during the stirring granulation. Manufacturing method.

[0014]

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[In the formula, Rf represents a saturated or unsaturated alkyl group containing at least one fluorine atom, and X ₀
Is a sulfonamide,

[0016]

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Wherein Y ₀ is an alkylene oxide group,
Represents an alkylene group, and Rf 'represents a saturated or unsaturated hydrocarbon group containing at least one fluorine atom. Furthermore, A is _{-SO 3 M, -OSO 3 M,} -COOM, -OP
Represents a hydrophilic group such as O ₃ (M ₁ ) (M ₂ ), —PO ₃ (M ₁ ) (M ₂ ), and M, M ₁ and M ₂ are H, Li, K, Na or NH ₄
And m represents 0 or 1, n represents 0 or an integer of 1 to 10. ]

[0018]

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Wherein R ₁ represents an alkyl group or an alkenyl group, R ₂ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group, and R ₃ and R ₄ independently represent a hydrogen atom, a hydroxyl group, an alkyl group or COOM ₄ (M ₄ represents a hydrogen atom or an alkali metal atom), and X represents —CO— or —S
Represents O ₂ —, and Y represents —O—, —S— or —CONR ₅ —
(R ₅ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group), M ₃ represents a hydrogen atom or an alkali metal atom, l is 0 or 1, m ₁ is an integer of 0 to 2, and n ₁ is 1
Represents an integer of 1 to 3. ]

[0020]

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[Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent an alkyl group, an aralkyl group, an alkenyl group, a styryl group, a cinnamyl group, and l ₁ , l ₂ , l ₃ , l _4, l ₅ each represents an integer of 0 or 1, n ₂ represents an integer of 2 to 100. However, when R ³ is an alkyl group and l ₃ is 1, at least one of l ₁ , l ₂ , l ₄ , and l ₅ is 1.
When l ₁ , l ₂ , l ₃ , l ₄ , and l ₅ are 0, the corresponding R ¹ , R
² , R ³ , R ⁴ and R ⁵ are hydrogen atoms. ]

[0022]

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[Wherein, R represents an alkyl group having 4 to 25 carbon atoms which may have a linear or branched substituent or

[0024]

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(Wherein R ₁₁ and R ₁₂ each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and l ₁₀ represents an integer of 0 to 4). n ₃ and m ₃ each represent 0 or an integer of 1 to 25, but are not 0 at the same time. A ₃ and B ₃ are respectively

[0026]

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Wherein n ₁₁ , m ₁₁ and l ₁₁ each represent 0, 1, 2 or 3, but n ₁₁ and m ₁₁ in A ₃ and B ₃ Are not simultaneously 0, and when n ₃ or m ₃ is 0, m ₁₁ is not 0.]

[0028]

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[0029] wherein, R ₂₁ represents a monovalent organic group, R ₂₂
Represents an ethylene group or a propylene group, and m ₂₁ is 4 to 5
Represents an integer of 0. X ₂₁ represents a hydrogen atom, —SO ₃ M ₂₁ or —PO ₃ M ₂₁ . Here, M ₂₁ represents a hydrogen atom, an alkali metal atom or —NH ₄ . ] Formula (VI) _{R 6 - (O) x S} y O z M 6 wherein, R ₆ represents a substituted or unsubstituted aliphatic group, an aromatic group or a heterocyclic group, x is 0 or 1 , Y is 1 or 2, z
Represents an integer of 2 to 8, and M ₆ represents a cation. (2) The granule according to the above (1), wherein the amount of at least one of the compounds represented by the general formulas [I] to [VI] is 5 wt% or less based on the solid amount to be added. Manufacturing method.

(3) The method for producing granules according to (1) or (2), wherein the stirring granulation uses at least one liquid binder.

(4) The addition rate of the liquid binder is as follows:
The method for producing granules according to any one of the above items 1 to 3, wherein the granules are added at a rate of 4 g / min or less per kg of the solid to be added.

(5) The granules described above, wherein the granules are used in a solid processing agent for a silver halide photographic light-sensitive material.
5. The method for producing a granule according to any one of claims 4 to 4.

(6) The solid processing agent for a silver halide photographic light-sensitive material is at least one selected from the group consisting of inorganic carbonates, p-phenylenediamine derivatives, iron salts of polyaminocarboxylic acids, thiosulfates, hydroquinones and erythorbates. 6. The method for producing granules according to the above item 5, comprising a seed.

(7) When the raw material powder of the inorganic carbonate is used in a granulation step, particles having a particle size of 125 μm or less are 50 wt% or less of the whole inorganic carbonate raw material. 7. The method for producing granules according to 6.

(8) The solid processing agent for a silver halide photographic light-sensitive material is a granule,
The method for producing a granule according to any one of claims 7 to 13.

(9) The solid processing agent for a silver halide photographic light-sensitive material is a tablet.
The method for producing granules according to any one of the above.

The present invention will be described in more detail. An object of the stirring granulation method according to the present invention is to suppress the temperature rise due to friction heat due to stirring or heat of dissolution due to the addition of water being accumulated in the granules themselves (hereinafter referred to as heat storage), and a part of the granules is suppressed. Whether the granulation process can be controlled so as to stably stop the growth of the granules when the granules have grown to a desired particle size while preventing the dissolution of the granules, the continuous production stability and the granulation scale. This was an issue for upsizing.

However, when producing granules by the stirring granulation method, heat is generated by friction between the stirring blade and the powder particles or between the powder particles, or the powder particles enter between the stirring blade and the wall or bottom surface of the granulator. The generation of local frictional heat on the wall surface and the bottom surface due to this is physically inevitable. In addition, when the temperature of the granules rises due to these heat generations, the progress of granulation is further promoted, and at the same time, the viscosity of the granules is also increased. As a result, the phenomenon of causing a vicious cycle in which the generation of frictional heat is further promoted occurs. As a result, the progress of granulation accelerated at an accelerated rate, and the granules became uncontrollable and the whole granules solidified in a rice cake-like shape, causing a problem that the stirring blade was stopped and the granules could not be taken out of the granulator.

This problem has been remarkable when granulation is continuously performed by the same granulator. To solve this problem, conventionally, it is necessary to wash, wash and dry between batches of granulation. Met. On the other hand, the temperature rise of the granules due to the generation of these frictional heats during the stirring granulation tended to increase as the batch scale of the granulator became larger. For this reason, the batch scale of the granulator was restricted, and mass production could not be performed at once.

However, during the granulation step, the above-mentioned general formula [I]
When at least one of the compounds represented by the formulas (VI) to (VI) is added, it is estimated that the friction coefficient decreases due to the compound adhering to the stirring blade surface, the powder particle surface, and the inner wall surface of the granulator. However, the temperature rise of the granules due to frictional heat was effectively suppressed. As a result, the phenomenon that a part of the granules is dissolved is also prevented, the adhesion of the inner surface of the granulator is also eliminated, and the granulation progresses at an accelerated speed, and the granulation can be performed at a desired particle size without becoming uncontrollable. Now you can stop and end stably.

As a result, continuous production was made possible without washing with water between batches. In addition, since it became possible to increase the size of the granulator and the batch scale, the productivity was dramatically improved, and it was possible to produce inexpensive granules in large quantities. It has also been found that the granules thus produced have a surprising effect of improving storage stability and further increasing the dissolution rate.

Further, when tablets are produced by compression molding using the granules produced in this way, not only the kissing and sticking of the punches during compression molding are reduced, but also the hardness, even when high-speed compression is performed, is achieved. In addition to obtaining a friability, it was also found that there was a surprising effect of improving the storage stability of the tablet and increasing the dissolution rate.

Hereinafter, the granulation according to the present invention will be described. Granulation refers to an operation of forming a substantially uniform shape and size from a powdery, massive, or solution-type original. As a granulation method,
There are known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation, and the granulation method of the solid processing agent of the present invention. Is a stirring granulation method.

The stirring granulation method in the present invention will be described. The stirring granulation method is a method utilizing the cohesiveness of powder. That is, it is a method generally excellent in mixability in which the powder raw material placed in a fixed container is granulated while being stirred by a stirring blade. In the stirring granulation method, there are two forces, a force for aggregating the powder particles (hereinafter, this force is referred to as an adhesive force) and a force for separating the powder particles (hereinafter, this force is referred to as a separating force). The balance of the force determines the size of the granules. The adhesive force is proportional to the surface area of the particles, ie, the square of the particle diameter, and the separating force is proportional to the weight of the particles, ie, the cube of the particle diameter. Therefore, if the particle diameter of the powder is small in the initial stage of granulation, the adhesion becomes greater than the separation force, and the granulation proceeds and the particles grow. Since it becomes a force, even if the particles come into contact with each other, they are immediately separated and the progress of granulation is stopped. The point at which the progress of granulation stops is referred to as the granulation end point. If the granules do not grow to the desired particle size only by the adhesive force between the powder particles, the particle size of the granules at the end point of granulation can be increased by adding a liquid binder or heating the granules. Or you may be.

The range indicated by the granulation step in the present invention is as follows:
This refers to the entire process from the start of charging the raw material into the device to the removal of the granules grown to a desired particle size from the device and transfer to a container, or immediately before transport to the next step. The raw materials also include the compounds represented by the general formulas [I] to [VI] in the present invention. The apparatus used in the granulation step may be a single apparatus, or may be used in combination with a plurality of apparatuses for the purpose of heating, cooling, or drying granules. Alternatively, the granules may be transferred between the apparatuses.

In the present invention, the compounds represented by the general formulas [I] to [VI] exert their effects even when added at any time during the granulation step. That is, the general formula [I]
~ The compound represented by (VI) may be added to the apparatus in advance and then other materials may be added, or stirring may be started to agglomerate the powder particles to increase the particle diameter. It may be added inside or after the end of granulation. Preferably,
If the compounds represented by the general formulas [I] to [VI] are added during the period from the start of stirring to the end point of the granulation, the effects of the present invention are more favorably exhibited.

In the present invention, the compounds represented by the general formulas [I] to [VI] to be added during the granulation step are added in powder form during the granulation step. The powder to be added is preferably fine particles, and as a particle diameter, 90% or more of the total weight is preferably 125 microns or less.

Next, the general formulas [I] to [V
The compound represented by I] will be described below.

In the above formula (I), Rf represents a saturated or unsaturated alkyl group containing at least one fluorine atom (for example, an alkyl group, an alkenyl group, an alkynyl group), and preferably has 4 to 12 carbon atoms. Preferably it is a C6-C9 alkyl group. A is preferably-
SO ₃ M, and M, M ₁ and M ₂ are preferably Li,
K and Na are most preferably Li. m is 0 or 1, n
Represents 0 or an integer of 1 to 10, preferably m = 0,
n = 0.

The representative compounds represented by the general formula [I] are shown below, but are not limited thereto.

[0051]

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[0052]

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Among the above compounds, particularly preferred compounds are
(I-1), (I-2) and (I-4).

These compounds can be synthesized by a usual method and are also available as commercial products.

In the general formula [II], R ₁ is preferably a straight-chain or branched alkyl or alkenyl group having 5 to 20 carbon atoms, and R ₂ is preferably a hydrogen atom, a straight-chain having 1 to 5 carbon atoms. It is a chain or branched alkyl group or a hydroxyalkyl group.

Next, specific examples of the compound represented by the general formula [II] are shown below.

[0057]

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[0058]

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[0059]

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[0060]

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In addition to the above compounds, JP-A-62-56961
Compounds [II] -1 to 55 described on pages 4 to 6 can also be used.

The above exemplified compounds are known compounds or are commercially available and can be obtained by ordinary routes.

The compound (surfactant) represented by the general formula [III] or [IV] will be described. General formula (III)
In the above, the alkyl group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ has 1 to 20 carbon atoms, and may be any of a chain and a cyclic, Straight-chain,
Including branched ones, specifically, for example, methyl, ethyl,
n-propyl, i-propyl, butyl, t-butyl, s
ec-butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, octadecyl and the like. The aralkyl group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ has 7 to 20 carbon atoms, and specifically includes, for example, benzyl, phenethyl, dibenzyl, 2-naphthylmethyl and the like. Groups.

The alkenyl group represented by R ¹ , R ² , R ³ , R ⁴ and R ⁵ has 3 to 20 carbon atoms, and specifically includes, for example, allyl, 4-hexenyl, 4-decenyl, 9-
Each group such as octadecenyl is exemplified.

The aromatic ring of the aralkyl group and styryl group may have a substituent. Examples of the substituent include an alkyl group (for example, each group such as methyl, ethyl, propyl, t-amyl, nonyl, etc.) and an alkoxy group. Groups (e.g., methoxy, ethoxy, propoxy, 2-ethoxyethoxy, etc.) and aryloxy groups (e.g., phenoxy, p-tolyloxy, o-chlorophenoxy, etc.). Specifically, for example, p-methoxybenzyl, 2,
4-dimethylbenzyl, p-phenoxyphenethyl, p
-Butyl styrene and the like.

Examples of the compound represented by the general formula [III] or [IV] are shown below.

[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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In the general formula [V], R ₂₁ is a monovalent organic group, for example, having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms.
Hexyl, heptyl, octyl,
Represents nonyl, decyl, undecyl or dodecyl;
Or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, and the substituent preferably has 3 carbon atoms.
~ 12 alkyl groups, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
Represents undecyl or dodecyl. The aryl group is phenyl, tolyl, xinyl, biphenyl or naphthyl, and is preferably phenyl or tolyl. The position where the alkyl group is bonded to the aryl group may be any of the ortho, meta and para positions. R ₂₂ represents an ethylene group or a propylene group.

The specific examples of the compounds represented by the formula [V] are shown below.

[0075]

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[0076]

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In the general formula [VI], examples of the aliphatic group represented by R ₆ include an alkyl group, an alkenyl group and an alkynyl group. Examples of the alkyl group include methyl,
Examples include groups such as ethyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, and dodecyl. These alkyl groups further include a halogen atom (for example, a halogen atom such as chlorine, bromine or fluorine), an alkoxy group (for example, methoxy,
Ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy, etc.), aryloxy group (eg, phenoxy, naphthyloxy, etc.), aryl group (eg, phenyl, naphthyl, etc.), alkoxycarbonyl Groups (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl, etc.), aryloxycarbonyl groups (eg, phenoxycarbonyl, naphthyloxycarbonyl, etc.), alkenyl groups (eg, vinyl, allyl, etc.) Group), heterocyclic group (for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, morpholyl, piperidine, piperazyl, pyrimidine, pyrazoline, furyl, etc.), alkynyl group (for example, propargyl group, etc.), amino group (for example, Amino, N, N-di Chiruamino, each group anilino), a cyano group, sulfonamido group (e.g., methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octyl sulfonylamino, may be substituted by each group) such as phenylsulfonylamino.

Examples of the alkenyl group include a vinyl group,
Examples include an allyl group and the like, and examples of the alkynyl group include a propargyl group.

Examples of the aromatic group represented by R ₆ include a phenyl group and a naphthyl group.

Examples of the heterocyclic group represented by R ₆ include a pyridyl group (each group such as 2-pyridyl, 3-pyridyl and 4-pyridyl), a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group and a phenyl group. , A pyrrolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a selenazolyl group, a sulfolanyl group, a pipedilinyl group, a pyrazolyl group, a tetrazolyl group, and the like.

The alkenyl group, alkynyl group, aromatic group and heterocyclic group are all the alkyl group represented by R ₆ , the substituents of the alkyl group, the groups shown as the substituted atoms, groups similar to the atoms, It can be replaced by an atom.

The cation represented by M ₆ is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. Examples of the organic cation include an ammonium ion (each ion such as ammonium, tetramethylammonium, and tetrabutylammonium) and a phosphonium ion (eg, tetraphenylphosphonium). Ion), guanidyl ion and the like.

Specific examples of the compound represented by the general formula [VI] are shown below, but the present invention is not limited thereto.

VI-1 C ₂ H ₅ SO ₃ Na VI-2 CH ₃ (CH ₂ ) ₆ SO ₃ Na VI-3 CH ₃ (CH ₂ ) ₇ SO ₃ Na VI-4 CH ₃ (CH ₂ ) ₅ OSO _{3 Na VI-5 CH 3 (} CH 2) 6 OSO 3 Na VI-6 CH 3 (CH 2) 7 OSO 3 Na VI-7 CH 3 O (CH 2) 2 SO 3 Na

[0085]

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VI-14 CH ₃ (CH ₂ ) ₅ SO ₃ Na The amount of the compounds represented by the general formulas [I] to [VI] in the present invention is not particularly limited. When the content is 5 wt% or less, the effects of the present invention are more favorably exhibited from the viewpoint of long-term storage stability and dissolution rate of the granules.

In the solid processing agent of the present invention, the preferred particle size (particle size) of the solid particles after granulation is in the range of 0.1 μm to 1.5 mm for 60% or more of the total weight, and more preferably, for the total weight. Is in the range of 0.1 μm to 1.5 mm, and particularly preferably, 80% or more of the total weight is 0.1 μm to 1.5 mm.
It is preferably from μm to 1.5 mm.

Methods for measuring the particle size of the granular particles include, for example, a sieving method, a microscopic method, a Coulter counter method, a sedimentation method, a centrifugal method, a wind sieving method, a diffusion method, and an adsorption method. "Powder Engineering (Basic)", Kawakita, Koishi,
It is described in Taniya co-author, Maki Shoten (issued in 1973). The particle size (particle size) in the present invention refers to a value measured by a sieving method, and a value of an average particle size of a particle size distribution obtained by the sieving method.

[0089] The specific volume of the granular solid processing agent in the present invention, 0.7cm ³ /g~2.8cm ³ / g are preferred.
0.7 cm ³ / g is not preferable a longer dissolution time that it follows, 2.8 cm ³ / g or more but an unfavorable fines during handling tends to occur. The scope of the present invention is preferable because the dissolution time is short and the amount of generated fine powder is small.

In the present invention, the rotation speed of the stirring blade is 50 to 50.
5000 rpm is good, preferably 100-3000 r
pm, more preferably 300 to 2,000 rpm
It is. If the rotation speed is low, it takes time to mix, which is not preferable in terms of cost. On the other hand, if the number of rotations is high, the granules for producing the tablet-like solid processing agent become too hard, so that a tablet-like solid treatment agent having the target hardness and friability cannot be produced. The scope of the present invention is a range in which productivity is high in terms of cost and hardness and friability of the tablet-like solid processing agent are good.

The liquid binder in the present invention will be described. The binder is a material added to increase the adhesion between the powder particles. Therefore, generally, during the granulation step, it is added before the end point of the granulation is reached. The binder may be added in a solid or liquid state.
The liquid binder refers to both those which are liquid when added during the granulation step and those which are solid at the time of addition and which physically change during the granulation step and become liquefied. The compound used as a liquid binder is water, an organic solvent, a solution obtained by dissolving a binder in water or an organic solvent, or a liquid binder obtained by heating or pressurizing a solid binder at room temperature, alone or in combination of two or more. It was done. Examples of the binder used for the liquid binder are shown below, but the present invention is not limited thereto.

Examples of the binder used for the liquid binder of the present invention include saccharides and compounds represented by the following general formula (2).

The saccharide referred to in the present invention refers to monosaccharides, polysaccharides in which a plurality of these are glycosidically bonded to each other, and degradation products thereof.

Monosaccharides include single polyhydroxy aldehydes, polyhydroxy ketones and their reduced derivatives,
It is a general term for a wide range of derivatives such as oxidized derivatives, deoxy derivatives, amino derivatives and thio derivatives. Many sugar, is represented by the general formula C _n H _2n O _n, a compound derived from a sugar skeleton represented by the general formula be included, in the present invention is defined as monosaccharides. Preferred among these monosaccharides are
These are sugar alcohols in which the aldehyde group and ketone group of the sugar are reduced to primary and secondary alcohol groups, respectively.

The polysaccharides include celluloses, starches,
Glycogens and the like are included, celluloses include derivatives such as cellulose ethers in which some or all of the hydroxyl groups are etherified, and starches are various degradation products from hydrolysis to maltose. Including certain dextrins. Cellulose may be in the form of an alkali metal salt from the viewpoint of solubility. Those preferably used as these polysaccharides are celluloses, dextrins and cyclodextrins, and more preferably cyclodextrins.

Specific examples of monosaccharides are shown below.

(1) Glyceraldehyde (2) Dihydroxyacetone (including dimer) (3) D-erythrose (4) L-erythrose (5) D-threose (6) L-threose (7) D- Ribose (8) L-ribose (9) D-arabinose (10) L-arabinose (11) D-xylose (12) L-xylose (13) D-lyxose (14) L-lyxose (15) D-xylulose ( 16) L-xylulose (17) D-ribulose (18) L-ribulose (19) 2-deoxy-D-ribose (20) D-allose (21) L-allose (22) D-altrose (23) L -Altrose (24) D-glucose (25) L-glucose (26) D-mannose (27) L-manno (28) D-growth (29) L-growth (30) D-idose (31) L-idose (32) D-galactose (33) L-galactose (34) D-talose (35) L-talose ( 36) D-Kinobose (37) Digitarose (38) Digitoxose (39) Shimarose (40) D-sorbose (41) L-sorbose (42) D-tagatose (43) D-fucose (44) L-fucose (45) 2-deoxy-D-glucose (46) D-psicose (47) D-fructose (48) L-fructose (49) L-rhamnose (50) D-glucosamine (51) D-galactosamine (52) D-mannosamine ( 53) D-glycero-D-galactoheptose (54) D-glycero-D- Mannoheptose (55) D-glycero-L-mannoheptose (56) D-glycero-D-gloheptose (57) D-glycero-D-idoheptose (58) D-glycero-L-glucoheptose (59) D-glycero-L- Talloheptose (60) D-altroheptulose (61) D-mannoheptulose (62) D-altro-3-heptulose (63) D-glucuronic acid (64) L-glucuronic acid (65) N-acetyl- D-glucosamine (66) Glycerin (67) D-trait (68) L-trait (69) Erythrit (trade name, Mitsubishi Chemical Food Erythritol) (70) D-arabit (71) L-arabit (72) Adnit (73) ) Xylit (74) D-Sorbit (75) L Sorbit (76) D-mannit (77) L-mannit (78) D-idit (79) L-idit (80) D-talit (81) L-talit (82) Zurcit (83) Allozurcit Among them, sugar alcohols preferably used are (66) to (83), and more preferably (69) and (74) to (83).

Specific examples of polysaccharides and sugar decomposed products are shown below.

(1) Maltose (2) Cellobiose (3) Trehalose (4) Gentiobiose (5) Isomaltose (6) Lactose (7) Raffinose (8) Gentianose (9) Stachyose (10) Xylan (11) Araban (12) ) Glycogen (13) dextran (14) inulin (15) levan (16) galactan (17) agarose (18) amylose (19) sucrose (20) agarobiose (21) methylcellulose (22) dimethylcellulose (23) trimethylcellulose (24) ) Ethyl cellulose (25) Diethyl cellulose (26) Triethyl cellulose (27) Carboxymethyl cellulose (28) Carboxyethyl cellulose (29) Aminoethyl cellulose (30) Droxymethylcellulose (31) Hydroxyethylmethylcellulose (32) Hydroxypropylcellulose (33) Hydroxypropylmethylcellulose (34) Hydroxypropylmethylcellulose acetate succinate (35) Carboxymethylhydroxyethylcellulose (36) α-dextrin (37) β-dextrin ( 38) γ-dextrin (39) σ-dextrin (40) ε-dextrin (41) α-limit dextrin (42) β-limit dextrin (43) phosphorylase limit dextrin (44) soluble starch (45) thin nori starch (46) ) White dextrin (47) Yellow dextrin (48) British gum (49) α-cyclodextrin (50) β-cyclodex Phosphorus (51) γ-cyclodextrin (52) methyl-α-cyclodextrin (53) methyl-β-cyclodextrin (54) methyl-γ-cyclodextrin (55) hydroxypropyl-α-cyclodextrin (56) hydroxypropyl -Β-cyclodextrin (57) Hydroxypropyl-γ-cyclodextrin (58) Maltocyclodextrin Saccharides exist widely and naturally, and commercially available products can be easily obtained. Also, various derivatives can be easily synthesized by performing reduction, oxidation, dehydration, or the like.

As commercially available products, cyclodextrins such as α-100H and β-100 manufactured by Shimizu Port Refining Co., Ltd.
γ-100, K-100, Isoelite P, Isoelite PH, Methyl-β-CD, Hydroxypropyl-β-
Pine flow, Paindex series, Foodtex, Max 100, Glister P, TK-16, manufactured by Matsutani Chemical Industry Co., Ltd.
MPD, H-PDX, Stakodex, NOF Corporation
Oil Q series manufactured by the company.

In the present invention, a compound represented by the following general formula (2) can also be preferably used.

Formula (2) HO- (A ¹ -O) l ^1- (A ² -O) l ^2- (A ³ -O)
l in ³ -H ^{formula, A 1, A 2, A} 3 is substituted independently represent an unsubstituted straight chain or branched alkylene group, which may optionally be the same or different.

Further, examples of the substituent include a hydroxy group, a carboxy group, a sulfonyl group, an alkoxy group, a carbamoyl group and a sulfamoyl group. Those preferably used are those in which A ¹ , A ² and A ³ are each unsubstituted. Most preferably, A ¹ , A ² ,
A ³ is _{-CH 2 CH 2 -, - CH} (CH 3) -CH 2 - is.

L ¹ , l ² and l ³ are each 0 or 0
Represents an integer of 500. Here, l ¹ + l ² + l ³ ≧ 5.

Of these, at least one of l ¹ , l ² , and l ³ is preferably 15 or more, and more preferably 20 or more.

When the compound represented by the general formula (2) in the present invention is, for example, a copolymer obtained by mixing and copolymerizing two kinds of monomers a and b, those having the following arrangement are also included. Is done.

-Aba-ba-ba-a-ba-b-a-a-ba-a-b-b-a-a-a-a-a-a-a-b -Ba- -a-aa-a-a-a-a-b-a-b-b-b-b-b-a-a-a-a- Among the copolymers which can be used as these copolymers, A preferable compound is a block polymer (pluronic non-ion) of ethylene glycol and propylene glycol represented by the following general formula (2-1).

Formula (2-1) HO— (CH ₂ CH ₂ —O) l ⁴ — [CH (CH ₃ ) CH ₂
—O] l ⁵ — (CH ₂ CH ₂ —O) l ⁶ —H In the formula, l ⁴ , l ⁵ and l ⁶ are l ¹ ,
It is synonymous with l ² and l ³ .

In the compound represented by formula (2-1) in the present invention, the content (% by weight) of ethylene oxide in the total molecular weight is preferably at least 70% by weight, particularly preferably at least 80% by weight. Things.

Hereinafter, general formulas (2) and (2-
The specific compound represented by 1) is shown.

HO— (CH ₂ —CH ₂ —O) _n ′ -H average molecular weight 2-1 300 2-2 600 2-3 1000 2-4 1500 2500 2-5 2000 2-6 3000 2-7 4000 2- 8 6000 2-9 10000 2-10 15000 2-11 20000 2-12 30000 HO- (CH 2 CH 2 -O) a '- [CH (CH ₃₎ -CH ₂ -O] b' - (CH ₂ CH _2- O) c'-H Content (% by weight) of ethylene oxide average molecular weight in total molecules 2-1-1 80 8350 2-1-2 80 10800 2-1-3 50 4600 2-1-4 70 6500 2-1-5 80 5000 2-1-6 50 3500 2-1-7 70 7850 2-1-8 50 4150 In the above formula, n ′ represents an integer of 5 or more, and a ′, b ′,
c 'has the same meaning as l ¹ , l ² and l ³ .

Among the compounds represented by formulas (2) and (2-1) in the present invention, the most preferred compound is polyethylene glycol (sometimes referred to as PEG).

In the case of polyethylene glycol,
Those having an average molecular weight in the range of 2,000 to 20,000 are preferred, and those in the range of 3,000 to 15,000 are particularly preferred.

When adding the liquid binder, the liquid binder may be dropped as it is, but it is preferable to spray using a spray nozzle. The rate of addition of the liquid binder in the present invention is preferably less than 4 g / min per kg of solid added. That is, within the range of the addition rate, it is estimated that the liquid binder is uniformly dispersed in the raw material, but it has been found that there is an effect of suppressing generation of frictional heat. In addition, the generation of large particles and the generation of fine powder were reduced, and the variation width of the particle size distribution of the granules was reduced. Further, the granules are excellent in compression moldability, and tablets having excellent hardness and friability can be obtained without occurrence of punch spots or sticking.

Examples of the color developing agent used in the color developing agent of the present invention include p-phenylenediamine derivatives (hereinafter, also referred to as p-phenylenediamine compounds).
In particular, a p-phenylenediamine-based compound having a water-soluble group is preferably used because it exhibits the desired effects of the present invention and has little fogging.

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the photosensitive material and has less skin contamination than a para-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. Not only has the advantage that the skin is less irritating,
In particular, the object of the present invention can be more efficiently achieved by combining with the color developing solution of the present invention.

The water-soluble group has at least one amino group on the amino group or benzene nucleus of the p-phenylenediamine compound.
Specific examples of the water-soluble group include — (CH ₂ ) _n —CH ₂ OH, — (CH ₂ ) _m —NHSO ₂ — (CH ₂ ) _n CH ₃ , and — (CH ₂ ) _{m -O- (CH 2) n -CH 3} , - (CH 2 CH 2 O) n C m H 2m + 1 (m and n each is 0
Represents the above integer. ), - COOH group, and as -SO ₃ H group and the like.

Specific examples of the color developing agent preferably used in the present invention include compounds (C-1) to (C-1) described in JP-A-4-86674, pp. 26-31.
(C-16).

The above color developing agents are usually used in the form of salts such as hydrochloride, sulfate and p-toluenesulfonate.

The above color developing agents may be used alone or in combination of two or more. If desired, a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-methyl-1-agent may be used.
It may be used in combination with phenyl-3-pyrazolidone or methol.

In the present invention, when the color developer according to the present invention contains the compounds represented by the following general formulas [A] and [B], the effects of the present invention are more favorably exhibited. .

That is, when a solid processing agent is used, not only the storage stability of the tablet is improved but also the strength of the tablet can be maintained as compared with other compounds. There is also an advantage that less fog occurs.

[0123]

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[0124] In the general formula [A], R ₃₁ and R ₃₂ are each an alkyl group is not a hydrogen atom at the same time, an aryl group, represents an R'-CO- or a hydrogen atom, R ₃₁ and R
_The alkyl group represented by ₃₂ may be the same or different,
Each is preferably an alkyl group having 1 to 3 carbon atoms. Further, these alkyl groups may have a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, or a hydroxyl group.

R 'represents an alkoxy group, an alkyl group or an aryl group. The alkyl group and the aryl group of R ₃₁ , R ₃₂ and R ′ include those having a substituent, and R ₃₁ and R ₃₂ may combine to form a ring, for example, piperidine, pyridine, triazine and morpholine. And a heterocyclic ring such as

[0126]

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In the formula, R ¹¹ , R ¹² and R ¹³ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R ¹⁴ represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted group. Represents a substituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group, or amino group. The heterocyclic group is a 5- to 6-membered ring and is composed of C, H, O, N, S and a halogen atom, and may be saturated or unsaturated. R ¹⁵ is -CO-, -S
O ₂ - or -C (= NH) - represents a divalent group selected from, n _{3 1} is 0 or 1. In particular, when n ₃₁ = 0, R ¹⁴ represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R ¹³ and R ¹⁴ may form a heterocyclic group together.

Specific examples of the hydroxylamine compound represented by the general formula [A] are described in US Pat. No. 3,287,12.
Nos. 5, 33, 293, 034 and 3, 287, 1
No. 24, etc., and particularly preferred specific exemplary compounds are described in JP-A-4-86641, No. 36.
(A-1) to (A-39) described on pages 38 to 38 and JP-A-Hei 3
(1) to (5) described on pages 3 to 6 of JP-A-33845.
3) and (1) to (52) described in JP-A-3-63646, pp. 5-7.

Next, specific examples of the compound represented by the above general formula [B] are described in JP-A-4-86641, Nos. 40-43.
(B-1) to (B-33) described on page 3 and JP-A-3-33
No. 846, pages 4 to 6 (1) to (56).

The compounds represented by the general formulas [A] and [B] are usually free amines, hydrochlorides, sulfates,
It is used in the form of p-toluenesulfonate, oxalate, phosphate, acetate and the like.

In the color developer and black-and-white developer used in the present invention, a trace amount of sulfite can be used as a preservative. Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

It is necessary to use a buffer for the color developer and the black-and-white developer used in the present invention. Examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate and trisodium phosphate. , Tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate , 5
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like.

Examples of the development accelerator include JP-B-37-160.
Nos. 88, 37-5987, 38-7826, 44-12380, 45-9019 and U.S. Pat. No. 3,813,247; No. 50-15554
Quaternary ammonium salts represented by JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429. US Patent 2,61
P-aminophenols described in U.S. Pat. Nos. 0,122 and 4,119,462; U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796 and 3,253. No. 919, JP-B-41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, and the like. 42-25201
No. 3,128,183, JP-B-41-11
Nos. 431 and 42-23883 and U.S. Pat.
2,501 or the like, a polyalkylene oxide,
In addition, 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles and the like can be added as necessary.

The color developing agent preferably does not substantially contain benzyl alcohol. Substantially means not more than 2.0 ml, more preferably not containing at all, 1 liter of color developer. The one that does not substantially contain changes in photographic characteristics during continuous processing, especially the increase in stain is small,
More favorable results are obtained.

For the purpose of preventing fog and the like, chlorine ions and bromine ions are required in the color developer in the processing tank. In the present invention, preferably 1.0 × 10 ⁻² as chlorine ions.
~ 1.5 × 10 ^-1 mol / l, more preferably 4 × 10 ^-2
１1 × 10 ⁻¹ mol / l. Chlorine ion concentration is 1.
If it is more than 5 × 10 ^-1 mol / l, it is not preferable to feed the development and quickly obtain a high maximum density. Also, 1.0 × 1
If the amount is less than 0 ^-2 mol / l, stain is generated, and furthermore, photographic properties (especially, minimum density) accompanying continuous processing are undesirably large. Therefore, it is necessary to adjust the solid processing agent so that the color developer in the processing tank has the above-mentioned concentration range.

In the present invention, bromine ions are preferably contained in the color developing solution in the processing tank in a range of 3.0 × 10 ^{-3 to} 1.0 ×.
It contains 10 ^-3 mol / l. More preferably 5.0 × 10
^{−3 to} 5 × 10 ⁻⁴ mol / l. Particularly preferably 1 × 1
0 ^{-4 to} 3 × 10 ^-4 mol / l. Bromine ion concentration of 1
When the amount is more than × 10 ⁻³ mol / l, the development is delayed, the maximum density and the sensitivity are lowered. When the amount is less than 3.0 × 10 ⁻³ mol / l, stain is generated, and the photographic property is changed due to continuous processing. (Particularly the minimum density) is not preferred. As in the case of chloride ions, it is necessary to adjust the bromine concentration in the solid processing agent so as to be within the above range.

When directly added to a color developing agent, sodium chloride, potassium chloride,
Ammonium chloride, nickel chloride, magnesium chloride,
Manganese chloride, calcium chloride, and cadmium chloride are mentioned, and preferred are sodium chloride and potassium chloride.

The color developing agent and the fluorescent whitening agent added to the developing agent may be supplied in the form of a counter salt. As bromine ion supply substances, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide,
Cadmium bromide, cerium bromide and thallium bromide are preferred, of which potassium bromide and sodium bromide are preferred.

The color developer and the developer used in the present invention may optionally contain an antifoggant in addition to chloride ions and bromine ions. As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Representative examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

It is preferable that a triazinylstilbene-based fluorescent whitening agent is contained in the color developer and the developer used in the present invention from the viewpoint of the effects of the present invention. The addition amount of these compounds is 0.2 g to 10 g per liter of the color developing solution.
It is preferable to adjust the solid processing agent so as to fall within the range described above, and more preferably in the range of 0.4 g to 5 g.

Further, the color developer and the black-and-white developer composition used in the present invention may contain, if necessary, methylcellosolve, methanol, acetone, dimethylformamide,
β-cyclodextrin, and other Japanese Patent Publication No. 47-3337
The compounds described in JP-A Nos. 8 and 44-9509 can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developer can be used together with the developing agent. As these auxiliary developers, for example, methol, phenidone, N, N-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known. I have.

Further, various additives such as a stain inhibitor, an anti-sludge agent and a layering effect promoter can be used.

The color developer and the black-and-white developer composition are described in JP-A-4-118649, from page 63, bottom to eighth.
From page 64 to page 64, from the bottom to the third line, the chelating agents represented by the following general formula [K] and the exemplified compounds K-1 to K-2.
Addition of 2 is preferable from the viewpoint of effectively achieving the object of the present invention.

Of these chelating agents, K
-2, K-9, K-12, K-13, K-17, K-1
9 are preferably used, and in particular, K-2 and K-
No. 9 exhibits the effect of the present invention well.

It is preferable that the chelating agent is added to the solid processing agent in an amount of 0.1 to 20 g per liter of the color developer and the black-and-white developer, more preferably 0.2 to 8 g. It is.

Further, the color developing agent and the solid processing agent for black and white development may contain anionic, cationic, amphoteric and nonionic surfactants.

Further, if necessary, an alkyl sulfonic acid,
Various surfactants such as arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added.

The bleaching agent preferably used in the bleaching agent or the bleach-fixing agent according to the present invention is a ferric complex salt of an organic acid.

Since the ferric complex salt of an organic acid has a high bleaching ability, it does not need to be used in a small amount when it is solidified, so that not only can the tablet be reduced in weight and size, but also the tablet can be preserved when formed into a tablet. It has the effect of improving the properties, and is preferably used in the present invention.

Preferred specific examples of the ferric complex salt of an organic acid are shown below.

[0152]

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[0153]

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As the ferric complex salts of the compounds (C-1) to (C-12), sodium, potassium or ammonium salts of these ferric complex salts can be arbitrarily used. From the viewpoint of the effect of the object of the present invention and the solubility, ammonium salts of these ferric complex salts are preferably used.

Among the above compound examples, those particularly preferably used in the present invention include (C-1), (C-3),
(C-4), (C-5) and (C-9), and particularly preferred is (C-1).

In the present invention, as the bleaching agent or the bleach-fixing agent, besides the iron complex salt of the compound represented by the general formula [C], a ferric complex salt of the following compound can be used as a bleaching agent.

[A'-1] Ethylenediaminetetraacetic acid [A'-2] Trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] Dihydroxyethylglycinic acid [A'-4] Ethylenediaminetetrakismethylenephosphonic acid [A'-4] A'-5] Nitrilotrismethylene phosphonic acid [A'-6] Diethylenetriamine pentakismethylenephosphonic acid [A'-7] Diethylenetriaminepentaacetic acid [A'-8] Ethylenediamine diorthohydroxyphenylacetic acid [A'-9] Hydroxy Ethylethylenediaminetriacetic acid [A'-10] Ethylenediaminedipropionic acid [A'-11] Ethylenediaminediacetic acid [A'-12] Hydroxyethyliminodiacetic acid [A'-13] Nitrilotriacetic acid [A'-14] Nitrilotri Propionic acid [A'-15] tri Tylenetetramine hexaacetic acid [A'-16] Ethylenediaminetetrapropionic acid [A'-17] β-alanine diacetic acid The amount of the ferric organic acid complex is 0.01 mol to 2 mol / l of bleaching solution or bleach-fixing solution. It is preferably contained in the range of 0 mol, more preferably 0.05 to 1.5 mol /
1 range. Therefore, it is necessary to adjust the solid processing agent so that the concentration of the organic acid ferric complex in the bleaching solution or bleach-fixing solution in the processing tank falls within the above range.

Examples of the bleaching agent, the bleach-fixing agent and the fixing agent include imidazole and derivatives thereof described in JP-A-64-295258 and the general formulas [I] to [IX] described in the same specification.
By containing at least one of the compounds represented by the following formulas and these exemplified compounds, an effect can be exerted on the rapidity.

In addition to the above accelerators, JP-A-62-1234
Illustrative compounds described on pages 51 to 115 of JP-A-59-59, and exemplified compounds described on pages 22 to 25 of JP-A-63-17445, and JP-A-53-9563.
Nos. 0 and 53-28426 can be used in the same manner.

The bleaching agent or bleach-fixing agent may contain, in addition to the above, halides such as ammonium bromide, potassium bromide and sodium bromide, various optical brighteners, defoamers and surfactants. it can.

As the fixing agent used in the fixing agent or the bleach-fixing agent in the present invention, thiocyanates and thiosulfates are preferably used. The content of the thiocyanate is at least 0.1 mol / l per liter of the fixing solution or the bleach-fixing solution.
More preferably, when processing a color negative film,
It is more preferably at least 0.5 mol / l, particularly preferably at least 1.0 mol / l. The content of the thiosulfate is preferably at least 0.2 mol / l, and more preferably 0.5 mol / l or more when a color negative film is processed. In the present invention, the object of the present invention can be more effectively achieved by using a combination of a thiocyanate and a thiosulfate.

The fixing agent or bleach-fixing agent used in the present invention may contain, alone or two or more kinds of pH buffers consisting of various salts, in addition to these fixing agents. Further, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride, ammonium bromide and the like. Compounds known to be added to ordinary fixing agents or bleach-fixing agents, such as alkylamines and polyethylene oxides, can be added as appropriate.

A fixing agent or a bleach-fixing agent is disclosed in
No. 295258, p. 56, the general formula [F
It is preferable to add the compound represented by the formula A) and the exemplified compound, which not only exerts the effects of the present invention better, but also occurs in a processing solution having a fixing ability when a small amount of photosensitive material is processed for a long period of time. Another effect is that the amount of sludge to be produced is extremely small.

The compound represented by the formula [FA] described in the same specification can be prepared by a general method as described in US Pat. No. 3,335,161 and US Pat. No. 3,260,718. Can be synthesized. These compounds may be used alone or in combination of two or more.

Good results can be obtained when the amount of these compounds is in the range of 0.1 to 200 g per liter of the fixing solution or the bleach-fixing solution.

In the present invention, the stabilizer preferably contains a chelating agent having a chelate stability constant of 8 or more for ferric ions. Here, the chelate stability constant is defined as L.C. G. FIG. Silen A. E. FIG. Martell
Written, "Stability Constants of
Metal-ion Complexes ", The
Chemical Society, London (1
964). S. Chaberek A. E. FIG. Marte
II, "Organic Sequestering"
Agents ", Wiley (1959) and the like.

As a chelating agent having a chelating stability constant for ferric ion of 8 or more, Japanese Patent Application No. 2-2347
Nos. 76 and 1-324507.

The amount of the chelating agent used is preferably 0.01 to 50 g per liter of the stabilizing solution, more preferably 0.05 to 50 g.
Good results are obtained in the range of ２０20 g.

Preferred compounds to be added to the stabilizing solution include ammonium compounds. These are supplied by ammonium salts of various inorganic compounds. The amount of the ammonium compound added is 0.001 per liter of the stabilizing solution.
The range is preferably from mol to 2.0 mol, and more preferably from 0.002 to 1.0 mol.

Further, the stabilizer preferably contains a sulfite.

Further, the stabilizer preferably contains a metal salt in combination with the chelating agent. Examples of such metal salts include Ba, Ca, Ce, Co, In, La, and M.
n, Ni, Bi, Pb, Sn, Zn, Ti, Zr, M
g, Al or Sr metal salts, which can be supplied as inorganic salts such as halides, hydroxides, sulfates, carbonates, phosphates, acetates and the like, or as water-soluble chelating agents. The amount used is preferably in the range of 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably in the range of 4 × 10 ^-4 to 2 × 10 ^-2 mol, per liter of the stabilizing solution.

To the stabilizing solution, an organic acid salt (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), a pH adjusting agent (phosphate, borate, hydrochloric acid, sulfate, etc.) are added. can do. In the present invention, known fungicides can be used alone or in combination as long as the effects of the present invention are not impaired.

It is preferable to use deionized water for the stabilizing solution. Further, a reverse osmosis membrane is used for low replenishment, and the solution having a high salt concentration is returned to the first tank of the fixing or bleach-fixing solution and the stabilizing solution. A method of returning a liquid having a low salt concentration to the final tank of the stable liquid is also a preferable embodiment for carrying out the present invention.

The developing agent that can be used in the black-and-white developing tablet of the present invention preferably contains reductones.

Specific examples of reductones will be shown below.

[0176]

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[0177]

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[0178]

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Of the reductones, particularly preferred are ascorbic acid and / or erythorbic acid (stereoisomer) represented by D-1 and salts thereof.

Further, the following developing agents may be contained. Dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, dichlorohydroquinone, isopropylhydroquinone,
Methylhydroquinone, 2,3-dichlorohydroquinone, methoxyhydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, etc. 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1- Phenyl-4-methyl-3-pyrazolidone, 1
-Phenyl-4,4-dimethyl-3-pyrazolidone, 1
-Phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
Pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1
-Phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1- (2-benzothiazole) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, etc., aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), 1-allyl-
3-aminopyrazolines (for example, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p
-Amino-m-methylphenyl) -3-aminopyrazoline), pyrazolones (eg, 4-aminopyrazolone), and mixtures thereof.

The developing tablets preferably contain a sulfite and / or metabisulfite. Further, when the tablet is dissolved to form a developer, the amount of sulfite in the solution is 0.05 mol / L or more and less than 0.3 mol / L, and further 0.1 mol / L.
It is preferably at least liter and less than 0.3 mol / liter.

In addition, as a buffer (for example, carbonate, boric acid, borate, alkanolamine, etc.), an alkaline agent,
Dissolution aids (eg, polyethylene glycols and esters thereof), pH adjusters (eg, organic acids such as citric acid), sensitizers (eg, quaternary ammonium salts), development accelerators, hardeners (eg, Dialdehydes such as glutaraldehyde), a surfactant, and an azole organic antifoggant as an antifoggant (eg, indazole, imidazole, benzimidazole, triazole, benztriazole, tetrazole, thiadiazole) A concealing agent for concealing calcium ions mixed in tap water used in the treatment liquid, sodium hexametaphosphate, calcium hexametaphosphate,
A polyphosphate, ethylene triaminepentaacetic acid, or the like may be contained. Furthermore, silver stain preventives, for example, JP-A-56-24
No. 347 can also be used.

The pH of the developing solution obtained from the developing tablet is 10.
It is preferably in the range of 5 or less, more preferably 9-1.
It is in the range of 0.0.

The developing solution obtained from the developing tablet is described in
An amino compound such as an alkanolamine described in No. 6-106244 can be used.

In addition, the developer obtained by using the developing tablet of the present invention includes L.P. F. A. Meson, "Photographic Processing Chemistry", Focal Press (1966), pp. 22-229, U.S. Pat.
3,015, 2,592,364, JP-A-48-48
No. 64933 may be used.

On the other hand, a carbonate having a buffering action is preferable as the alkaline agent. As carbonates, potassium carbonate,
Examples include sodium carbonate and lithium carbonate. Furthermore,
The amount of carbonate in the developing solution is preferably 0.3 mol / L or more and less than 0.8 mol / L.

Next, the fixing solution used in the present invention will be described.

The fixing solution used in the present invention is preferably prepared by dissolving and preparing a solid processing agent. The fixing agent preferably contains a thiosulfate as a fixing agent. The thiosulfate is specifically used as a salt of lithium, potassium, sodium, or ammonium. Preferably, a fixing solution having a high fixing speed can be obtained by using ammonium thiosulfate and sodium thiosulfate.

In addition, iodide salts and thiocyanates can also be used as fixing agents. The fixing solution used in the present invention contains a sulfite. As sulfites,
Solid lithium, potassium, sodium, ammonium salts and the like are used.

The fixing solution used in the present invention may contain a water-soluble chromium salt or a water-soluble aluminum salt. Examples of the water-soluble chromium salt include chromium alum, and examples of the water-soluble aluminum salt include aluminum sulfate, potassium aluminum chloride, and aluminum chloride.

The fixer used in the present invention contains acetate ions. The type of acetate ion is arbitrary, and the present invention can be applied to any compound that dissociates acetate ion in the fixing solution.However, acetic acid and lithium, potassium, sodium, and ammonium salts of acetic acid are preferably used. Sodium salts and ammonium salts are preferred.

Further, citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid and optical isomers thereof may be contained.

These salts include, for example, potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, potassium tartrate, sodium hydrogen tartrate, sodium tartrate, ammonium hydrogen tartrate, ammonium potassium tartrate And lithium, potassium, sodium and ammonium salts represented by sodium potassium tartrate, sodium malate, ammonium malate, sodium succinate, ammonium succinate and the like.

Among the above compounds, more preferred are citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof. Other acids include, for example, salts of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic acid, propionic acid and oxalic acid, and preferably boric acid and aminopolycarboxylic acids. Acids and salts.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the surfactant include anionic surfactants such as sulfated and sulfonated compounds, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants. Examples of the wetting agent include alkanolamine and alkylene glycol.

Examples of the fixing accelerator include thiourea derivatives, alcohols having a triple bond in the molecule, thioethers and the like.

The fixing solution has a pH of at least 3.8, preferably at least 4.
2 to 5.5.

Further, the replenishment rate during the processing according to the present invention is preferably 20 ml / 4 or less for both the developing solution and the fixing solution in the sense that the waste liquid amount is reduced, and more preferably 15 ml / 4.

[0200]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 A developer for printing was manufactured according to the following procedure. However, the types and amounts of additives added during the granulation step were changed as shown in Table 1.

Injection developer (1) Preparation of granule A1 Group 1 hydroquinone 116.16 kg Group 2 8-mercaptoadenine 0.53 kg 1,2,3-benzotriazole 1.26 kg Sodium erythorbate 29.04 kg Dimezone S 6 .29 kg Sodium sulfite 34.22 kg Sorbitol 9.34 kg Group 3 The compounds of the present invention described in Table 1 and the amount added Liquid binder Pure water 1.60 kg Sodium octanesulfonate 16.00 g <Operation 1> Mitsui Henschel mixer FM-500J ( (Mitsui Metals Co., Ltd.) and crushed and mixed at a rotation speed of 950 rpm for 5 minutes.

<Operation 2> Next, two groups were added, and the
Mix at 00 rpm for 30 seconds.

<Operation 3> Next, the liquid binder is rotated at a rotation speed of 3
The mixture was kneaded for 3 minutes while being added at 00 rpm over 2 minutes.

<Operation 4> Next, at a rotational speed of 600 rpm,
Kneaded for minutes.

<Operation 5> Next, the inside of the granulator was
r, and dried under reduced pressure for 40 minutes at 300 rpm. On the way, three groups were added during drying under reduced pressure.

Thus, granule A1 was prepared.

(2) Preparation of Granule B1 Group 1 Diethylenetriaminepentasodium pentasodium 5.00 kg Potassium carbonate 47.64 kg Sodium carbonate monohydrate 14.27 kg Potassium bromide 2.30 kg 1-phenyl-5-mercapto-1, 2,3,4-tetrazole 68.74 g lithium hydroxide monohydrate 9.63 kg mannitol 11.50 kg sorbitol 4.61 kg sodium sulfite 68.48 kg 2 group Compounds of the present invention listed in Table 1 and the amount added Liquid binder Pure water 1.98 kg Sodium octanesulfonate 19.80 g <Operation 1> One group was added to Mitsui Henschel mixer FM-500J (manufactured by Mitsui Kinzoku Co., Ltd.), and premixed at 215 rpm for 30 seconds.

<Operation 2> Next, the liquid binder was rotated at a rotation speed of 2
The mixture was kneaded for 15 minutes while adding at 15 rpm for 2.5 minutes.

<Operation 3> Next, three groups were added, and the
Mix for 10 minutes at 15 rpm.

Thus, granule B1 was prepared.

<Number of Continuous Batches> The above operation was continuously granulated for 10 batches, and the number of continuous batches not requiring water washing between the granulated batches was evaluated.

<Dissolution state, dissolution time> Granules A1: 166 g were sealed in an aluminum bag Granules B1: 615 g were sealed in an aluminum bag.

After storing these granules at a high temperature of 60 ° C. for 10 days, open them, first dissolve the granules A1, then the granules B1, in about 3200 ml of water, and the dissolution state and dissolution time at that time Was measured.

Dissolution appearance A: When the aluminum bag is opened, there is no scattering of powder. Dissolution is smooth ○: When opening the aluminum bag, a very small amount of powder was scattered, but no mask was required for work. Dissolution is also smooth. △: When opening the aluminum bag, a small amount of powder is scattered, so it is better to use a mask when working. There are also many agglomerates, which collect at the bottom during dissolution. However, there is no problem in practical use. ×: When the aluminum bag is opened, powder is scattered and a mask is required. Agglomeration of agglomerated granules is also a problem. XX: The greater the number of "X", the greater the amount of scattered powder.
In addition, agglomeration of the agglomerated granules is large and it takes time to dissolve.

Table 1 shows the above results.

<Dot Quality when Developing Photographic Material for Printing> Using a solution whose dissolution was confirmed as a development replenisher, an image setter DTR3075 manufactured by Dainippon Screen Co., Ltd., an automatic developing machine LD-T1100 A running process was performed using a processing apparatus connected and docked (manufactured by Dainippon Screen Co., Ltd.) until replenishment was performed in an amount three times the developing tank capacity. As a photosensitive material, a Konica Graphic Arts film HSH was used.

The processing conditions and the replenishment amounts of the respective processing agents are as follows.

[0219] At this time, the purifying agent was directly charged into the washing tank.

<Evaluation of halftone dot quality> 1 from Image Setter Jenna Set 3075 manufactured by Dainippon Screen Co., Ltd.
75L. A halftone dot of 50% was output, and the halftone quality was visually evaluated using a 100-fold loupe according to the following five grades.

◎: No fringe at all, and smooth dot quality. ：: No fringe is observed, but the border of dot is slightly rough. Δ: Slight fringe, lower limit level for practical use of dot. ×: The fringe is clearly visible. XX: The fringe is severe, and there is a fogging silver between dots. The above results are shown in Table 1.

[0222]

[Table 1]

As is clear from Table 1, when the compound of the present invention was added, the stability of continuous batch, the dissolution state and dissolution time after storage at a high temperature, and the time when the photosensitive material for printing was developed. It can be seen that the halftone dot quality is significantly improved.

Example 2 Tough Press Collect 1527HU manufactured by Kikusui Seisakusho using the granules A1 and B1 prepared in Example 1
(Tablet making machine, tableting machine) The tablet A1: 9.7 g and the tablet B: 13.6 g, respectively, and the tablet A1 and the tablet B1 each having a diameter of 30 mm were weighed per tablet.

<Appearance at the time of tableting> Adhesion and creaking of the punch at the time of tableting were observed, and the “appearance at the time of tableting” was evaluated as follows.

◎: Very good without sticking and no creaking of the punch. ：: Very small amount of sticking of the punch but no problem. Good without creaking of the punch. Δ: There was no sticking but no practical problem. This is a practical problem, and there is a slight creaking of the punch. ××: If the number of “x” increases, the amount of the punch attached increases, and the creaking of the punch also becomes severe. <Kutsuki after dissolution and solubility> Tablet A1: 17, Tablet B1: 45 in aluminum pack
Samples were placed separately from each other, and samples into which each was mixed were prepared, sealed, and stored at 60 ° C. for 10 days. After storage, the aluminum pack was opened, and the number of pills on the tablet, and first, tablet A1, then tablet B1
Was dissolved in about 3200 ml of water in this order, and the dissolution time at that time and the state of dissolution were observed, and "Kutsuki after storage and solubility" were evaluated as follows.

◎: No dustiness and good dissolution. が あ る: Weak dustiness but no problem in dissolution. Δ: 2 to 5 sets of dusty tablets, no problem in dissolution. X: 10 pieces of dusty tablets. As described above, there is a problem of solidification at the bottom at the time of dissolution. XX: An increase in the number of “X” indicates that the state of dustiness is worse. <Dot quality when developing photosensitive material for printing> Evaluation was performed in the same manner as described above.

Table 2 shows the above results.

[0229]

[Table 2]

As can be seen from Table 2, the present invention shows good adhesion to tablets and poor stickiness and solubility after storage at high temperatures, and furthermore, excellent dot quality when the photosensitive material for printing is developed. It can be seen that the effect is achieved.

Example 3 A medical developer was prepared according to the following procedure. However, the types and amounts of additives added during the granulation step, the addition rate of the liquid binder, and the amount of potassium carbonate particles having a particle diameter of 125 μm or less were changed as shown in Table 3.

(1) Preparation of Granule A2 Group 1 Sodium Erythorbic Acid 120.85 kg Sodium Metabisulfite 36.26 kg Phenidone 10.88 kg N-acetyl-penicillamine 0.24 kg Glutaraldehyde Sodium bisulfite 14.65 kg Sorbitol 15.12 kg Group 2 Compounds of the present invention described in Table 3 and the amounts added Liquid binder Pure water 1.66 kg Sodium octanesulfonate 16.60 g <Operation 1> Group 1 was added to Mitsui Henschel mixer FM-500J (manufactured by Mitsui Kinzoku Co., Ltd.). In addition, pre-mixing was performed for 30 seconds at a rotation speed of 300 rpm.

<Operation 2> Next, the liquid binder is rotated at a rotation speed of 3
The mixture was kneaded for 3 minutes while being added at 00 rpm over 2 minutes.

<Operation 3> Next, at 600 rpm,
Kneaded for minutes.

<Operation 4> Next, the inside of the granulator was
r, and dried under reduced pressure for 45 minutes at 300 rpm. On the way, two groups were added during drying under reduced pressure.

Thus, Granule A2 was prepared.

(2) Preparation of granule B2 Group 1 Compounds of the present invention described in Table 3 and the amounts added Group 2 Potassium carbonate 232.63 kg Sodium 3- (5-mercaptotetrazol-1-yl) benzenesulfonate 0. 99 kg diethylenetriaminepentaacetic acid 4.51 kg sorbitol 13.28 kg mannitol 45.01 kg liquid binder pure water 4.51 kg potassium iodide 157.41 g 5-mercapto-1-tetrazoyl-sodium acetate 224.91 g sodium octanesulfonate 45.10 g <operation 1> One group was added to a Mitsui Henschel mixer FM-500J (manufactured by Mitsui Kinzoku Co., Ltd.) so as to spread the granulator wall and the entire stirring blade.

<Operation 2> Next, two groups are added, and the number of rotations is set to 30.
Pre-mixed at 0 rpm for 30 seconds.

<Operation 3> Next, the liquid binder was rotated at a rotation speed of 3
While adding at the addition speed shown in Table 3 at 00 rpm, 4
Kneaded for 5 minutes.

Thus, granule B2 was prepared.

<Number of Continuous Batches> Evaluation was performed in the same manner as in Example 1.

<Dissolution state and dissolution time> Granule A2: 185 g was sealed in an aluminum bag. Granule B2: 374 g was sealed in an aluminum bag.

After storing these granules at a high temperature of 60 ° C. for 10 days, open them, dissolve them in granule A2 and then granule B2 in about 2800 ml of water in this order, and the dissolution state and dissolution time at that time Was measured. The evaluation was performed in the same manner as in Example 1.

<Evaluation of Photographic Quality when Developing Medical Photosensitive Material> A solution confirmed to be dissolved was used as a development replenisher, and an automatic developing machine using TCX-201 manufactured by Konica Corporation was used. 100 pieces of running processing were performed. The processing was performed at a developing temperature of 36 ° C., a fixing temperature of 35 ° C., a drying temperature of 55 ° C., and a processing time of dry to dry of 60 seconds. The replenishment amount is 180 ml /
It was m ^2. As a photosensitive material, Konica Medical Film SR-G was used after being uniformly exposed to light so that the optical density after development processing would be 1.0.

<Sensitometry Fluctuation> The film was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica) and a tube voltage of 90
X-ray irradiation was performed under the conditions of kVp, current of 20 mA, and time of 0.05 seconds, and a sensitometric curve was prepared by a distance method to determine the sensitivity. The sensitivity value (S ₂ ) was determined as the reciprocal of the X-ray dose required to obtain a density of fog + 1.0.

As the γ value, Fog + 0.25 to Fog +
In the density range of 2.0, the gradient was indicated by a slope obtained by dividing the density difference by the logarithmic value difference of the exposure amount required to obtain the density.
Also, the maximum density at which the exposure amount can be increased is shown as Dm.

From the sensitometric results obtained in this manner, the sensitometric variations due to the running process were evaluated according to the following five grades.

◎: no sensitometric fluctuation, stable quality ：: slight sensitometric fluctuation, but no practical problem Δ: sensitometric fluctuation, but practical Acceptable level limit x: Sensitometric fluctuation is greatly observed, and is not a practically acceptable level. XX: Sensitometric fluctuation is severe and greatly deviates from a practically acceptable level.

Table 3 shows the above results.

[0250]

[Table 3]

As is clear from Table 3, when the compound of the present invention was added, the stability of continuous batch, the dissolution and dissolution time after storage at high temperature, and the photographic performance when the medical light-sensitive material was subjected to running processing were improved. It can be seen that it is significantly improved.

When the rate of addition of the liquid binder is 4 g / min or less per 1 kg of the solid to be added, it can be seen that the effects of the present invention are exhibited more favorably.

In the raw material powder of the inorganic carbonate used in the granulation step, when the raw material powder is used in the granulation step, a particle diameter of 125%
It can be seen that the effect of the present invention is more excellent when the particle size of μm or less is 50 wt% or less of the whole inorganic carbonate raw material.

Example 4 Tough Press Collect 1527HU manufactured by Kikusui Seisakusho using the granules A2 and B2 prepared in Example 3
(Tablet making machine, tableting machine), the weight per tablet was tablet A2: 10.3 g, tablet B2: 12.5 g, respectively.
In each case, tablets A2 and B2 each having a diameter of 30 mm were produced.

<State of Tableting> Evaluation was performed in the same manner as in Example 2.

<Kuttsuki and Solubility after Storage> In addition, a sample in which 18 tablets A2 and 30 tablets B2 were separately placed in an aluminum pack and a sample in which each was mixed were placed in an aluminum pack. And sealed, 60 ° C
For 10 days. After storage, the aluminum pack is opened, and the number of clicks on the tablet, and first, the tablet A2,
Next, the tablet B2 was dissolved in water (about 2800 ml) in that order, the dissolution time at that time and the state of dissolution were observed, and the "stickiness and solubility after storage" were evaluated as follows.

Evaluation was performed in the same manner as in Example 2.

<Evaluation of Photographic Quality when Medical Photosensitive Material Was Developed> Evaluation was performed in the same manner as in Example 3.

The above results are shown in Tables 4 and 5.

[0260]

[Table 4]

[0261]

[Table 5]

As is clear from Tables 4 and 5, when the compound of the present invention was added, the adhesion at the time of tableting, the stickiness after storage at high temperature, the dissolution state and the dissolution time, and the running of the medical light-sensitive material were examined. It can be seen that the photographic performance when the test was performed was remarkably improved.

When the rate of addition of the liquid binder is 4 g / min or less per 1 kg of the solid to be added, it can be seen that the effects of the present invention are exhibited more favorably.

In the raw material powder of the inorganic carbonate used in the granulation step, when used in the granulation step, the particle diameter of
It can be seen that the effect of the present invention is more excellent when the particle size of μm or less is 50 wt% or less of the whole inorganic carbonate raw material.

Example 5 A medical fixing agent was prepared according to the following procedure. However, the types and amounts of additives added during the granulation step were changed as shown in Table 6.

(1) Preparation of granule A3 Group 1 Ammonium thiosulfate 175.93 kg Sodium metabisulfite 11.09 kg 3-mercapto-1,2,4-triazole 0.60 kg Pine flow 10.85 kg Books described in Table 6 Inventive compound and its addition amount of 20 wt% 2 group The present invention compound described in Table 6 and its addition amount of 80 wt% HS (manufactured by Konica Chemical Co., Ltd.) (Structural formula: HOCH ₂ CH ₂ SCH ₂ —CH ₂ SCH ₂₎ CH ₂ OH) 12.05 kg 3rd group Sodium acetic anhydride 33.14 kg Liquid binder Pure water 750.36 g Food Blue No. 1 (manufactured by Daiwa Kasei Co., Ltd.) 0.60 g Sodium octanesulfonate 7.50 g <Operation 1> Mitsui Henschel One group was added to a mixer FM-500J (manufactured by Mitsui Kinzoku Co., Ltd.) and pressed at 430 rpm for 1 minute It engaged.

<Operation 2> Next, the liquid binder was rotated at a rotation speed of 4
The mixture was kneaded for 1 minute while adding at 30 rpm over 45 seconds.

<Operation 3> Next, the two groups were added and mixed at a rotation speed of 215 rpm for 30 seconds.

<Operation 4> Next, three groups were added and mixed at a rotation speed of 215 rpm for 30 seconds.

Thus, granule A3 was prepared.

(2) Preparation of Granule B3 Group 1 Succinic acid 51.25 kg Tartaric acid 12.81 kg Boric acid 12.81 kg Sorbitol 4.92 kg Mannitol 10.66 kg Group 2 Dry aluminum sulfate 76.88 kg Sodium acetate 70.21 kg 3 Group The compounds of the present invention described in Table 6 and the amounts added The fourth group PEG # 4000 3.20 kg Liquid binder Pure water 750.08 g Food Blue No. 1 (manufactured by Daiwa Kasei Co., Ltd.) 1.69 g Sodium octanesulfonate 7.50 g <Operation 1> One group was added to Mitsui Henschel Mixer FM-500J (manufactured by Mitsui Kinzoku Co., Ltd.), and premixed at 215 rpm for 30 seconds.

<Operation 2> Next, the liquid binder is rotated at a rotational speed of 2
The mixture was kneaded for 1.5 minutes while being added at 15 rpm for 45 seconds.

<Operation 3> Next, the two groups were added and mixed at a rotation speed of 215 rpm for 30 seconds.

<Operation 4> Next, the three groups were added and mixed at a rotation speed of 215 rpm for 30 seconds.

<Operation 5> Next, 4 groups were added and mixed at a rotation speed of 215 rpm for 30 seconds.

Thus, granule B3 was prepared.

<Number of Continuous Batches> Evaluation was performed in the same manner as in Example 1.

<Dissolution state and dissolution time> Granule A3: 1034 g was sealed in an aluminum bag. Granule B3: 243 g was sealed in an aluminum bag. These granules were stored at 60 ° C. for 10 days at high temperature and then opened. Then, in the order of granule A3 and then granule B3, about 37
The solution was dissolved in 00 ml, and the dissolution state and the dissolution time at that time were measured. The evaluation was performed in the same manner as in Example 1. Table 6 shows the above results.

[0279]

[Table 6]

As is clear from Table 6, when the compound of the present invention was added, the stability of continuous batch, the dissolution after storage at high temperature, and the dissolution time were remarkably improved.

Example 6 Tough Press Collect 1527HU manufactured by Kikusui Seisakusho using the granules A3 and B3 prepared in Example 5
(Tablet manufacturing machine, tableting machine), each tablet A3: 10.7 g, tablet B3: 9.3 g, tablet A3 and tablet B3 each having a diameter of 30 mm were prepared.

<Tablet Appearance> Evaluation was performed in the same manner as in Example 2.

<Kutuki and Solubility after Storage> A sample in which 57 tablets A3 and 12 tablets B3 were separately placed in an aluminum pack, and a sample in which each was mixed were stored. And sealed, 60 ° C
For 10 days. After storage, the aluminum pack is opened, and the number of clicks on the tablet, and first, the tablet A3,
Next, tablet B3 was dissolved in about 3700 ml of water in that order, the dissolution time at that time and the state of dissolution were observed, and "Kutsuki after storage and solubility" were evaluated in the same manner as in Example 2. Table 7 shows the above results.

[0284]

[Table 7]

As is clear from Table 7, it can be seen that the present invention has an effect on the adhesion at the time of tableting, the sharpness after storage at high temperature, and the solubility.

Example 7 A developer for color paper was prepared according to the following procedure.
However, the type and amount of the additive added during the granulation step were changed as shown in Table 8.

(1) Preparation of Granule A4 Group 1 Potassium carbonate 99.00 kg Sodium sulfite 1.05 kg Diethylenetriaminepentasodium pentasodium 18.00 kg Sodium paratoluenesulfonate 39.00 kg N, N-diethylhydroxylamine-2,2 Disodium '-disulfonate 24.30 kg Tinopal SEP (manufactured by Ciba Geigy) 9.00 kg lithium hydroxide monohydrate 10.50 kg mannitol 15.00 kg PEG # 4000 30.00 kg 2 group The compounds of the present invention described in Table 8 and their compounds 50 wt% of added amount Group 3 CD-3 (manufactured by Merck) 43.50 kg Group 4 Compounds of the present invention described in Table 8 and 50 wt% of the added amount <Operation 1> Mitsui Henschel Mixer FM-500J (Mitsui Metals Co., Ltd.) )), Add 1 group, and Were pre-mixed for 30 seconds at 15 rpm.

<Operation 2> Next, while warming the granulator by circulating hot water of 60 ° C. through the water jacket,
The kneading was performed at a rotation speed of 215 rpm. At this time, kneading was performed until the granule temperature reached 55 ° C., and PEG # 4000 was melted to form a liquid binder.

<Operation 3> Next, the second group was added, and the granulator was cooled by circulating water at 10 ° C. through a water jacket.
And mixed until

<Operation 4> Next, three groups were added, and the
Mix for 15 seconds at 15 rpm.

<Operation 5> Next, 4 groups were added, and the
Mix for 15 seconds at 15 rpm.

[0292] Thus, a granule A4 was prepared.

<Number of Continuous Batches> Evaluation was performed in the same manner as in Example 1.

<Dissolution state, dissolution time> Granule A4: 97.42 g was placed in an aluminum bag and sealed.

After storing these granules at a high temperature of 60 ° C. for 10 days, they were opened, dissolved in about 800 ml of water, and the dissolution state and dissolution time were measured. The evaluation was performed in the same manner as in Example 1.

<Yellow Stain in Unexposed Area When Color Paper is Developed> Using the granules after high-temperature storage as a developing replenisher, using a Konica Color Processor Frendy 878J, three times the developing tank capacity Until replenishment was performed, a running process was performed. At this time,
Spectral absorption at 440 nm in the unexposed portion immediately after the start of the treatment and after the end was measured with a color analyzer, and the difference was determined as the yellow stain in the unexposed portion. The replenishing amount of the replenisher was the same as when a commercially available refilling agent for Konica Eco-Jet cartridge color paper was used. Konica Color QAA6 paper was used as the photosensitive material.

Table 8 shows the above results.

[0298]

[Table 8]

As is clear from Table 8, when the compound of the present invention was added, not only the stability of continuous batch but also the dissolution and dissolution time after storage at high temperature, and further, the color paper was developed. It can be seen that the prevention of yellow stain in the unexposed portions at that time is also remarkably improved.

Example 8 The granule A4 prepared in Example 7 was converted into a tablet A4 having a weight of 11.0 g and a diameter of 30 mm per tablet using a tough press collect 1527HU (tablet making machine, tableting machine) manufactured by Kikusui Seisakusho. Produced.

<State of Tableting> Evaluation was performed in the same manner as in Example 2.

<Kuttsuki and Solubility after Storage> Further, the prepared tablets were put into an aluminum pack, 18 tablets A4 each, sealed, and stored at 60 ° C. for 10 days. After storage, open the aluminum pack, dissolve the number of tablets in the tablet, and dissolve the tablet A4 in about 800 ml of water, observe the dissolution time at that time, and the state of dissolution.
"Solubility" was evaluated in the same manner as in Example 2.

<Yellow Stain in Unexposed Area when Color Paper is Developed> The same evaluation as in the method described in Example 7 was carried out using the tablet after storage at high temperature as a developing replenisher. Table 9 shows the above results.

[0304]

[Table 9]

As is evident from Table 9, the present invention is effective not only for sticking during tableting but also for preventing stickiness and solubility after storage at high temperatures and preventing yellow stain in unexposed areas. You can see that there is.

[0306]

According to the present invention, it is possible to provide a method for producing granules which is excellent in continuous production stability and can be mass-produced by a large-sized granulator when producing granules by a stirring granulation method.
In particular, it was possible to provide an inexpensive production method which is excellent in high-speed continuous productivity of a granular or tablet-like solid processing agent for a silver halide photographic light-sensitive material having excellent storage stability and excellent solubility.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroshi Yoshimoto 1st Sakuracho, Hino-shi, Tokyo Konica Stock Company In-house F-term (reference) 2H016 AE00 AE01 AF00 AF01 BK00 BK02 BL00 BL01 BL02 BL03 BL06 4D063 FF14 GA10 4G004 NA02

Claims (9)

[Claims] 1. A method for producing granules by stirring granulation, characterized in that at least one compound represented by the following general formulas (I) to (VI) is added during the stirring granulation. Production method. Embedded image [In the formula, Rf represents a saturated or unsaturated alkyl group containing at least one fluorine atom, and X ₀ is a sulfonamide; And Y ₀ represents an alkylene oxide group or an alkylene group, and Rf ′ represents a saturated or unsaturated hydrocarbon group containing at least one fluorine atom. A is -S
_{O 3 M, -OSO 3 M,} -COOM, -OPO 3 (M 1)
Represents a hydrophilic group such as (M ₂ ), -PO ₃ (M ₁ ) (M ₂ ),
M, M ₁ and M ₂ represent H, Li, K, Na or NH ₄ ,
m represents 0 or 1, and n represents 0 or an integer of 1 to 10. [Chemical formula 3] Wherein, R ₁ represents an alkyl or alkenyl group, R ₂
Represents a hydrogen atom, an alkyl group or a hydroxyalkyl group; R ₃ and R ₄ independently represent a hydrogen atom, a hydroxyl group, an alkyl group or —COOM ₄ (M ₄ represents a hydrogen atom or an alkali metal atom); -CO- or -SO ₂ - represents,
Y is -O -, - S-, or -CONR ₅ - (R ₅ represents a hydrogen atom, an alkyl group or hydroxyalkyl group) represents, M ₃ represents a hydrogen atom or an alkali metal atom, l is 0 or 1 , M ₁ represents an integer of 0 to 2, and n ₁ represents an integer of ₁ to 3. [Formula 4] [Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent an alkyl group, an aralkyl group, an alkenyl group, a styryl group, a cinnamyl group, and l ₁ , l ₂ , l ₃ , l ₄ , l ₅ represents an integer of 0 or 1, respectively, and n2 represents an integer of ₂ to 100. However, when R ³ is an alkyl group and l ₃ is 1, l ₁ ,
At least one of l ₂ , l ₄ and l ₅ is 1. l ₁ ,
When l ₂ , l ₃ , l ₄ , and l ₅ are 0, the corresponding R ¹ , R ² , R
³ , R ⁴ and R ⁵ are hydrogen atoms. [Chemical formula 5] [Wherein, R represents an alkyl group having 4 to 25 carbon atoms which may have a linear or branched substituent or The representative (where, R ₁₁ and R ₁₂ each represent an alkyl group having 1 to 20 carbon atoms that may have a hydrogen atom or a substituent, l ₁₀ is an integer of 0 to 4). n ₃ and m ₃ each represent 0 or an integer of 1 to 25, but are not 0 at the same time. A ₃ and B ₃ are respectively And may be the same or different (however,
n ₁₁ , m ₁₁ and l ₁₁ represent 0, 1, 2 or 3, respectively. However, when n ₁₁ and m ₁₁ in A ₃ and B ₃ are not simultaneously 0, and when n ₃ or m ₃ is 0, m ₁₁ does not become 0. Embedded image [In the formula, R ₂₁ represents a monovalent organic group, R ₂₂ represents an ethylene group or a propylene group, and m ₂₁ represents an integer of 4 to 50. X ₂₁ represents a hydrogen atom, —SO ₃ M ₂₁ or —PO ₃ M ₂₁ . Here, M ₂₁ represents a hydrogen atom, an alkali metal atom or —NH ₄ . ] Formula (VI) _{R 6 - (O) x S} y O z M 6 wherein, R ₆ represents a substituted or unsubstituted aliphatic group, an aromatic group or a heterocyclic group, x is 0 or 1 , Y is 1 or 2, z
Represents an integer of 2 to 8, and M ₆ represents a cation. ] 2. The compound according to claim 1, wherein the amount of at least one of the compounds represented by the general formulas [I] to [VI] is 5 wt% or less based on the amount of the solid added. A method for producing granules. 3. The agitation granulation uses at least one liquid binder.
A method for producing the granules according to the above. 4. The method for producing granules according to claim 1, wherein the liquid binder is added at a rate of 4 g / min or less per kg of the solid to be added. 5. The method according to claim 1, wherein the granules are used as a solid processing agent for a silver halide photographic light-sensitive material.
The method for producing granules according to any one of the above. 6. A solid processing agent for a silver halide photographic light-sensitive material, comprising: an inorganic carbonate, a p-phenylenediamine derivative,
The method for producing granules according to claim 5, characterized in that the granules contain at least one selected from the group consisting of iron salts of polyaminocarboxylic acids, thiosulfates, hydroquinones and erythorbates. 7. The method according to claim 5, wherein when the raw material powder of the inorganic carbonate is used in a granulation step, particles having a particle size of 125 μm or less account for 50 wt% or less of the whole inorganic carbonate raw material. 7. The method for producing granules according to 6. 8. The method according to claim 5, wherein the solid processing agent for a silver halide photographic material is a granule. 9. The method according to claim 5, wherein the solid processing agent for a silver halide photographic material is a tablet.